Tetrahydroindazolyl-benzoxazines, their production and use

ABSTRACT

A compound of the formula: ##STR1## wherein R 1  is a C 1  -C 6  alkyl group, a C 3  -C 7  alkenyl group, a C 3  -C 7  alkynyl group, a halo(C 1  -C 5 )alkyl group, a halo(C 3  -C 4 ) alkenyl group, a halo(C 3  -C 4 )alkynyl group, a C 1  -C 4  alkoxy(C 1  -C 2 )alkyl group, a C 1  -C 2  alkylthio(C 1  -C 2 )alkyl group and R 2  is a hydrogen atom or a methyl group, which is useful as a herbicide.

This application is a divisional of copending application Ser. No.071234,619, filed on Aug. 22, 1988 now U.S. Pat. No. 4,877,444

The present invention relates to tetrahydroindazolyl-benzoxazines, theirproduction, and use. More particularly, the invention relates to noveltetrahydroindazolylbenzoxazines, a process for producing them, and theiruse as herbicides.

U.S. Pat. No. 4,640,707 discloses certain oxazines useful as herbicides.Also, U.S. Pat. No. 4,670,043 discloses various tetrahydroindazolesuseful as herbicides. However, these known herbicides are not sufficientin herbicidal potency or have poor selectivity between crop plants andweeds. Their herbicidal activity is thus not necessarily satisfactory.

It has now been found that tetrahydroindazolylbenzoxazines of theformula: ##STR2## wherein R¹ is a C₁ -C₆ alkyl group, a C₃ -C₇ alkenylgroup, a C₃ -C₇ alkynyl group, a halo(C₁ -C₅) alkyl group, a halo(C₃-C₄)alkenyl group, a halo(C₃ -C₄)alkynyl group, a C₁ -C₄ alkoxy(C₁-C₂)alkyl group or a C₁ -C₂ alkylthio(C_(l) -C₂)alkyl group and R² is ahydrogen atom or a methyl group show a high herbicidal potency againstvarious weeds with a high selectivity between crop plants and weeds.Thus, they produce a strong herbicidal activity against a wide varietyof weeds including broad-leaved weeds, Graminaceous weeds,Commelinaceous weeds and Cyperaceous weeds in agricultural plowed fieldsby foliar or soil treatment without producing any material phytotoxicityon various agricultural crops such as corn, wheat, rice plant, soybeanand cotton. Examples of the broad-leaved weeds include wild buckwheat(Polygonum convolvulus), pale smartweed (Polygonum lapathifolium),common purslane (Portulaca oleracea), common chickweed (Stellariamedia), common lambsquarters (Chenopodium album), redroot pigweed(Amaranthus retroflexus), radish (Raphanus sativus), wild mustard(Sinapis arvensis), shepherdspurse (Capsella bursa-pastoris), hempsesbania (Sesbania exaltata), sicklepod (Cassia obtusifolia), velvetleaf(Abutilon theophrasti), prickly sida (Sida spinosa), field pansy (Violaarvensis), catchweed bedstraw (Galium aparine), ivyleaf morningglory(Ipomoea hederacea), tall morningglory (Ipomoea purpurea), fieldbindweed (Convolvulus arvensis), henbit (Lamium amplexicaure),jimsonweed (Datura stramonium), black nightshade (Solanum nigrum),persian speedwell (Veronica persica), common cocklebur (Xanthiumpensylvanicum), common sunflower (Helianthus annuus), scentlesschamomile (Matricaria perforata), corn marigold ( Chrysanthemumsegetum), etc. Examples of Graminaceous weeds include Japanese millet(Echinochloa frumentacea), barnyardgrass (Echinochloa crus-galli), greenfoxtail (Setaria viridis), large crabgrass (Digitaria sanguinalis),annual bluegrass (Poa annua), blackgrass (Alopecurus myosuroides), oats(Avena sativa), wild oats (Avena fatua), johnsongrass (Sorghumhalepense), quackgrass (Agropyron repens), bermudagrass (Cynodondactylon), etc. Examples of the Commelinaceous weeds include asiaticdayflower (Commelina communis), etc. Examples of the Cyperaceous weedsinclude rice flatsedge (Cyperus iria), etc.

The tetrahydroindazolyl-benzoxazines (I) of the invention are alsoeffective in exterminating paddy field weeds including Graminaceousweeds such as barnyardgrass (Echinochloa oryzicola), broad-leaved weedssuch as common falsepimpernel (Lindernia procumbens), indian toothcup(Rotala indica) and waterwort (Elatine triandra), Cyperaceous weeds suchas water nutgrass (Cyperus serotinus), hardstem bulrush (Scirpusjuncoides) and needle spikerush (Eleocharis acicularis), and others suchas monochoria (Monochoria vaginalis) and arrowhead (Sagittaria pygmaea)without producing any phytotoxicity to rice plants on floodingtreatment.

Among the tetrahydroindazolyl-benzoxazines (I), preferred are thosewherein R¹ is a C₃ -C₄ alkenyl group, a C₃ -C₄ alkynyl group, a halo(C₁-C₅) alkyl group or a halo(C₃ -C₄)alkenyl group and those wherein R² isa hydrogen atom, particularly those wherein R¹ is a C₃ -C₄ alkynyl groupor a halo(C₃ -C₄)alkenyl group and R² is a hydrogen atom. Typicalexamples of the preferred compounds are3-chloro-2-[7-fluoro-4-propargyl-2H-1,4-benzoxazin-3(4H)-on-6yl]-4,5,6,7-tetrahydro-2H-indazole,3-chloro-2-[7-fluoro-4-(1-butyn-3-yl)-2H-1,4-benzoxazin-3(4H)-on-6-yl]-4,5,6,7-tetrahydro-2H-indazole,3-chloro-2-[7-fluoro-4-(2-chloro-2-propenyl)-2H-1,4-benzoxazin-3(4H)-on-6yl]-4,5,6,7tetrahydro-2H-indazole,etc.

The tetrahydroindazolyl-benzoxazines (I) of the invention can beproduced by either one of the following procedures:

Procedure (A):1

The tetrahydroindazolyl-benzoxazine (I) is prepared by reacting acompound of the formula: ##STR3## wherein R² is as defined above with acompound of the formula:

    R.sup.1 -X                                                 (III)

wherein R¹ is as defined above and X is the residue of a strong acidexcluding a hydrogen atom therefrom such as a halogen atom (e.g.chlorine, bromine, iodine) or a sulfonyl group (e.g. methanesulfonyl,p-toluenesulfonyl).

The reaction is usually effected in the presence of an acid-bindingagent in an inert solvent at a temperature of about 0° to 60° C. for aperiod of about 0.5 to 3 hours.

Normally, the compound (III) and the acid-binding agent are usedrespectively in amounts of about 1.0 to 1.2 equivalents and of about 1.0to 1.2 equivalents to one equivalent of the compound (II). As theacid-binding agent, there may be used a base such as sodium hydroxide,potassium hydroxide, sodium carbonate, potassium carbonate or sodiumhydride. Examples of the inert solvent are aromatic hydrocarbons (e.g.benzene, toluene, xylene), ethers (e.g. diethyl ether, diisopropylether, dioxane, tetrahydrofuran, diethyleneglycol dimethyl ether), acidamides (e.g. formamide, N,N-dimethylformamide, acetamide), sulfurcompounds (e.g. dimethylsulfoxide, sulphorane), aqueous ammonia, etc.These may be used solely or in combination.

After completion of the reaction, the reaction mixture is subjected toan ordinary post-treatment. For instance, the reaction mixture is pouredinto water, and the precipitated crystals are collected by filtration.Alternatively, the reaction mixture is shaken in combination with waterand a water-immiscible organic solvent for extraction, and the extractis concentrated. If desired, any conventional purification proceduresuch as chromatography or recrystallization may be applied to theresulting product.

According to the above process, there are obtainable thetetrahydroindazolyl-benzoxazines (I) wherein R¹ is an alkyl group (e.g.methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl,hexyl), an alkenyl group (e.g. allyl, 1-methylallyl, 2-butenyl,1-methyl-2-butenyl, 3-methyl-2-butenyl, 1,3-dimethyl-2-butenyl,2,3-dimethyl-2-butenyl, 1,2,3-trimethyl-2-butenyl), an alkynyl group(e.g. propargyl, 1-methylpropargyl, 2-butynyl, 1-methyl-2-butynyl), analkoxyalkyl group (e.g. methoxymethyl, ethoxymethyl, propoxymethyl,butoxymethyl, 1-methoxyethyl, 1-ethoxyethyl, 2-methoxyethyl,2-ethoxyethyl, 2-propoxyethyl), a haloalkyl group (e.g. 2-fluoroethyl,1,1,2,2-tetrafluoroethyl, trifluoromethyl, 2-chloroethyl), a haloalkenylgroup (e.g. 2-chloroallyl, 3,3-dichloroallyl, 2,3,3-trichloroallyl), ahaloalkynyl group (e.g. 3-chloropropargyl, 3bromopropargyl), analkylthioalkyl group (e.g. methylthiomethyl), etc.

Procedure (B): 1

The tetrahydroindazolyl-benzoxazine (I) is also obtainable by reacting ahexahydroindazolyl-benzoxazine of the formula: ##STR4## wherein R¹ andR² are each as defined above with a chlorinating agent.

This reaction is normally carried out in a solvent at a temperature of80° to 200° C. for a period of 5 to 20 hours. The chlorinating agent maybe employed in an excessive amount to the intermediary product (IV).Examples of the chlorinating agent are phosphorus oxychloride, thionylchloride, phosgene, oxalic dichloride, trichloromethyl chloroformate,etc. Examples of the solvent are toluene, xylene, chloroform, etc.

The thus produced tetrahydroindazolyl-benzoxazine (I) may be subjectedto an ordinary post-treatment and, when desired, purified by a per seconventional procedure such as column chromatography orrecrystallization.

Typical embodiments for production of thetetrahydroindazolyl-benzoxazines (I) are illustratively shown in thefollowing Examples.

Example 1 Preparation of3-chloro-2-[4-ethyl-7-fluoro-2H-1,4-benzoxazin-3(4H)-on-6-yl]-4,5,6,7-tetrahydro-2H-indazole(Compound No. 1)

To a solution of3-chloro-2-[7-fluoro-2H-1,4-benzoxazin-3(4H)-on-6-yl]-4,5,6,7-tetrahydro-2H-indazole(1.0 g) in N,N-dimethylformamide (10 ml), sodium hydride (0.3 g) andethyl iodide (0.5 g) were successively added, and the resultant mixturewas heated at 50° to 60° C., followed by stirring for 3 hours. Thereaction mixture was poured into water, and the precipitated crystalswere collected by filtration an purified by silica gel columnchromatography using a mixture of ethyl acetate and hexane as an eluentto give Compound No. 1 (0.9 g). m.p., 101.5 ° -102.5° C.

EXAMPLE 2 Preparation of3-chloro-2-[7-fluoro-4-propargyl-2H-1,4-benzoxazin-3(4H)-on-6-yl]-4,5,6,7-tetrahydro-2H-indazole(Compound No. 4)

A mixture of2-(7-fluoro-4-propargyl-2H-1,4-benzoxazin-3(4H)-on-6-yl)-2,3,4,5,6,7-hexahydro-2H-indazol-3-one(1 g) and phosphorus oxychloride (0.7 g) was heated under reflux for 6hours. After cooling, the reaction mixture was dissolved in chloroform,washed with a 5 % sodium hydroxide solution and water, dried andconcentrated. The residue was purified by silica gel columnchromatography to give Compound No. 4 (0.3 g). m.p., 166 ° -167° C.

In the same manner as above the compounds (I) as shown in Table 1 wereobtained.

                  TABLE 1                                                         ______________________________________                                         ##STR5##                      (I)                                            Compound                                                                      No.     R.sup.1       R.sup.2 Physical property                               ______________________________________                                        1       C.sub.2 H.sub.5                                                                             H       m.p., 101.5-102.5° C.                    2       CH.sub.2 OCH.sub.3                                                                          H       m.p., 152-153° C.                        3       CH.sub.2 CHCH.sub.2                                                                         H       m.p., 131-132° C.                        4       CH.sub.2 CCH  H       m.p., 166-167° C.                        5       CH(CH.sub.3)CCH                                                                             H       n.sub.D.sup.26.9 1.5635                         6       CH(CH.sub.3)OCH.sub.3                                                                       H       m.p., 177-178° C.                        7       CH.sub.2 OC.sub.2 H.sub.5                                                                   H       m.p., 145-146° C.                        8       CH.sub.2 CH.sub.2 F                                                                         H       m.p., 146-147°0 C.                       9       CH(CH.sub.3)OC.sub. H.sub. 5                                                                H       n.sub.D.sup.27.8 1.5516                         10      CH.sub.2 CClCH.sub.2                                                                        H       m.p., 148-149° C.                        11      CH.sub.2 CCBr H       m.p., 159-160° C.                        12      CH.sub.2 SCH.sub.3                                                                          H       m.p., 166-167° C.                        13      C.sub.2 H.sub.5                                                                             CH.sub.3                                                                              m.p., 106-107° C.                        14      CH.sub.2 CCH  CH.sub.3                                                                              m.p., 154.5-155° C.                      ______________________________________                                    

The starting compound (II) or (IV) in the process of the invention maybe produced according to the following scheme: ##STR6## wherein R¹ andR² are each as defined above and R³ is a C₁ -C₅ alkyl group and R⁴ is ahydrogen atom, a C₁ -C₆ alkyl group, a C₃ -C₇ alkenyl group, a C₃ -C₇alkynyl group, a halo(C₁ -C₅)alkyl group, a halo (C₃ -C₄)alkenyl group,a halo(C₃ -C₄)alkynyl group, a C₁ -C₄ alkoxy(C₁ -C₂)alkyl group or a C₁-C₂ alkylthio(C₁ -C₂)alkyl group.

The reaction at each step in the above scheme will be hereinafterexplained in detail.

(1) Preparation of the compound (II) from the compound (V):1

The compound (II) can be obtained by subjecting the compound (V) toreductive cyclization. The reductive cyclization may be accomplished,for instance, by treatment of the compound (V) with a reducing agentsuch as iron powders or by catalytic reduction of the compound (V).

Treatment with iron powders may be carried out using iron powders in anamount of about 2.5 to 10 equivalents to one equivalent of the compound(V) in the presence of a small amount of an acid (e.g. acetic acid,chloric acid) in an inert solvent at a temperature of about 50° to 200°C. for a period of about 0.5 to 10 hours. Examples of the solvent aretoluene, 1,2-dichloroethane, methyl isobutyl ketone, acetic acid, water,etc. Their mixtures are also usable.

Catalytic reduction may be performed in the presence of a catalyticamount of palladium-carbon in an inert solvent (e.g. methanol, ethanol)at room temperature for a period of about 0.5 to 20 hours.

After completion of the reaction, the reaction mixture may be subjectedto an ordinary post-treatment. For instance, the reaction mixture isfiltered, the filtrate is combined with water, and the resultant mixtureis extracted with an organic solvent, followed by concentration. Whendesired, any conventional purification procedure such asrecrystallization or column chromatography may be applied to theresulting product.

A typical example for production of the compound (II) is illustrativelyshown in the following Example.

EXAMPLE 3

A suspension of3-chloro-2-(2-fluoro-4-butyloxycarbonylmethoxy-5-nitrophenyl)-4,5,6,7-tetrahydro-2H-indazole(10 g) and iron powders (10 g) in acetic acid was refluxed for 5 hours.After completion of the reaction, the reaction mixture was filtered bythe use of celite, and the filtrate was combined with water andextracted with ethyl acetate. The organic layer was concentrated, andthe residue was purified by column chromatography using a mixture ofhexane and ethyl acetate as an eluent to give3chloro-2-[7-fluoro-2H-1,4-benzoxazin-3(4H)-on-6yl]-4,5,6,7-tetrahydro-2H-indazole (6.2 g). n_(D) ²⁹.0 1.5628.

¹ H-NMR (δ, CDC1₃): 1.5-2.0 (br, 4H), 4.6 (s, 2H), 6.77 (d, 1H, J=11Hz), 6.92 (d, 1H, J=8 Hz), 9.8-10.1 (br, 1H).

In the same manner as above, there was obtained3-chloro-2-[7-fluoro-2-methyl-2H-1,4-benzoxazin-3(4H)-on-6-yl]-4,5,6,7-tetrahydro-2H-indazole.m.p., 189° C.

¹ H-NMR (δ, CDCl₃): 1.55 (d, 3H, J=7 Hz), 1.4-2.1 (br, 4H), 2.2-2.8 (br,4H), 4,62 q, 1H, J=7 Hz), 6.77 (d, 1H, J=10 Hz), 6.92 (d, 1H, J=8 Hz),9.9-10.2 (br, 1H).

(2) Preparation of the compound (V) from the compound (VI): 1

The compound (V) may be produced by reacting the compound (VI) with analpha-hydroxy acid alkyl ester of the formula: ##STR7## wherein R² andR³ are each as defined above, usually in the presence of a base in aninert solvent at a temperature of about 25 ° to 200° C. for a period ofabout 0.5 to 10 hours. In this reaction, the compound (XI) and the basemay be respectively used in amounts of about 1.0 to 1.2 equivalents andof about 1.0 to 4.0 equivalents to the compound (VI). As the base, theremay be used an inorganic base such as potassium fluoride, potassiumcarbonate or sodium hydride. Examples of the solvent are aromatichydrocarbons (e.g. toluene, xylene), halogenated hydrocarbons (e.g.dichloromethane, 1,2-dichloroethane), ethers (e.g. tetrahydrofuran,dioxane), etc.

After completion of the reaction, the reaction mixture is subjected toan ordinary post-treatment. For instance, the reaction mixture is pouredinto water, extracted with an organic solvent and concentrated. Ifdesired, any conventional purification procedure such as chromatographyor recrystallization may be adopted.

A typical embodiment for production of the compound (V) isillustratively shown in the following Example.

EXAMPLE 4

A suspension of3-chloro-2-(2,4-difluoro-5-nitrophenyl)-4,5,6,7-tetrahydro-2H-indazole(10 g), butyl glycollate (5 g) and potassium fluoride (10 g) in dioxane(30 g) was refluxed for 1 hour. After completion of the reaction, thereaction mixture was poured into water and extracted with ethyl acetate.The extract was dried over magnesium sulfate and concentrated. Theresidue was purified by liquid column chromatography using a mixture ofhexane and ethyl acetate as an eluent to give3-chloro-2-(2-fluoro-4-butyloxycarbonylmethoxy-5-nitro-phenyl)-4,5,6,7-tetrahydro-2H-indazole(10.2 g). m.p., 138° -139° C.

¹ H-NMR (δ, CDCl₃): 0.92 (t, 3H, J=6 Hz), 1.1-2.1 (br, 8H), 2.1-2.9 (br,4.2 (t, 2H, J=6 Hz), 4.8 (s, 2H), 6.82 (d, IH, J=11 Hz), 8.03 (d, 1H,J=8 Hz).

In the same manner as above, there was obtained3-chloro-2-[2-fluoro-4-(1-ethoxycarbonylethoxy-5-nitrophenyl]-4,5,6,7-tetrahydro-2H-indazole.n_(D) ²⁸.6 1.5671.

(3) Preparation of the compound (VI) from the compound (VII):

The compound (VI) is obtainable by nitrating the compound (VII) withnitric acid in conc. sulfuric acid normally at a temperature of about 0°to 30° C. for a period of about 0.3 to 3 hours. In the nitration, nitricacid is used in an amount of about 1.0 to 1.5 equivalents to thecompound (VII). Post-treatment of the reaction mixture after completionof the nitration may be carried out in a per se conventional manner.

A typical embodiment for production of the compound (VI) isillustratively shown in the following Example.

EXAMPLE 5

A solution of3-chloro-2-(2,4-difluorophenyl)4,5,6,7-tetrahydro-2H-indazole (217 g) inconc. sulfuric acid (1 kg) was cooled to 5° C., and 99 % nitric acid (67g) was dropwise added thereto at a temperature below about 10° C.,followed by stirring for 3 hours. After completion of the reaction, thereaction mixture was added to ice-water (10 kg), and the precipitatedcrystals were collected by filtration, washed and dried to give3-chloro-2-(2,4-difluoro-5-nitrophenyl)-4,5,6,7-tetrahydro-2H-indazole(227 g). m.p., 117° -118 ° C. (decomp.).

¹ H-NMR (δ, CDCl₃): 1.7-2.1 (br, 4H), 2.3-2.9 (br, 4H), 7.2 (t, 1H, J=10Hz), 8.28 (t, 1H, J=8 Hz).

The compound (VII) is obtainable according to the process as disclosedin U.S. Pat. No. 4,059,434.

(4) Preparation of the compound (II) from the compound (VIII): Thecompound (II) is obtainable from the compound (VIII) in the same manneras in Procedure (B).

Preparation of the compound (IV) or the compound (VIII) from thecompound (IX):

The compound (IV) or the compound (VIII) may be produced by reacting thecompound (IX) with a 2-alkoxycarbonylcyclohexanone of the formula:##STR8## wherein R⁵ is a C₁ -C₄ alkyl group.

This reaction may be carried out in a solvent at a temperature of 80° to200° C. for period of 0.5 to 20 hours. The compound (XII) is usuallyemployed in an amount of 1.0 to 1.2 equivalents to the compound (IX).Examples of the solvents are toluene, xylene, acetic acid, etc.

A typical embodiment for preparation of the compound (IV) isillustratively shown in the following example.

EXAMPLE 6

A mixture of7-fluoro-4-propargyl-2H-1,4-benzoxazin-3(4H)-on-6-ylhydrazine (1.8 g)and 2-ethoxycarbonylcyclohexanone (1.0 g) were dissolved in acetic acid(5 ml). The resultant mixture was heated under reflux for 8 hours. Aftercooling, the reaction mixture was concentrated under reduced pressure,and the residue was purified by silica gel column chromatography to give0.9 g of2-(7-fluoro-4-propargyl-2H-1,4-benzoxazin-3(4H)-on-6-yl)-2,3,4,5,6,7-hexahydro-2H-indazol-3-one.m.p., 189° -191° C.

Examples of the compound (IV) or the compound (VIII) produced in thesame manner as above are shown in Table 2.

                  TABLE 2                                                         ______________________________________                                         ##STR9##                (IV) or (VIII)                                       R.sup.2    R.sup.4       Physical property                                    ______________________________________                                        H          H             m.p., 218-220° C.                             H          C.sub.2 H.sub.5                                                                             m.p., 196-198° C.                             H          CH.sub.2 CCH  m.p., 189-191° C.                             CH.sub.3   CH.sub.2 CCH  m.p., 211-212° C.                             ______________________________________                                    

(6) Preparation of the compound (IX) from the compound (X):

The hydrazine (IX) is prepared from the aniline (X) according to themethod as described in J.Chem.Soc., (c), 1970, 2106. Namely, the aniline(X) is diazotiated by reacting with an alkali metal nitrite in an amountof 1.0 to 1.2 equivalents to the former in hydrochloric acid or sulfuricacid at a temperature of about -5 ° to 5° C. for a period of about 0.5to 24 hours. The resultant diazonium solution is then reacted withanhydrous stannous chloride in an amount of about 2 to 3 equivalents tothe aniline (X) at a temperature of about -20° to 50° C. for a period ofabout 0.5 to 3 hours. The reaction mixture is neutralized at atemperature lower than about 10° C. and extracted with an organicsolvent. The extract is dried and concentrated to give the hydrazine(IX). When desired, the product may be purified by recrystallization orcolumn chromatography.

A typical example for production of the hydrazine (IX) is illustrativelyshown in the following Example.

EXAMPLE 7

A suspension of 6-amino-7-fluoro-4-propargyl-2H1,4-benzoxazin-3(4H)-one(13.0 g) in conc. hydrochloric acid (70 g) was cooled to 0° to 5° C.,and a saturated solution of sodium nitrite (5.1 g) was dropwise addedthereto at 0° to 5° C., followed by stirring for 2 hours. The resultantmixture was cooled to -30° C., and a solution of anhydrous stannouschloride (28.1 g) in conc. hydrochloric acid (30 g) was added thereto atonce, followed by stirring at 0° to 5° C. for 3 hours. Celite (50 g) wasadded to the reaction mixture, which was neutralized with 10 % aqueoussodium hydroxide solution below 10° C. The resulting mixture wasfiltered, and the filtrate was extracted with ethyl acetate. The extractwas washed with water, dried and concentrated to give7-fluoro-4-propargyl-2H-1,4-benzoxazin-3(4H)-on-6 -ylhydrazine (8.2 g).

In the same manner as above, the compounds as shown in Table 3 wereobtained.

                  TABLE 3                                                         ______________________________________                                         ##STR10##                    (IX)                                            R.sup.2                                                                            R.sup.4      Physical property                                           ______________________________________                                        H    CH.sub.2 CCH m.p., 82-84° C. (decomp.)                                              .sup.1 H-NMR (δ, CDCl.sub.3 + d.sub.6 -DMSO):                           3.1-3.2(t, 1H, J=3Hz),                                                        3.7-4.2(br, 2H), 4.5(s,                                                       2H), 4.6(d, 2H, J=3Hz),                                                       6.2-6.7(br, 1H), 6.75(d,                                                      1H, J=12Hz), 7.05(d, 1H,                                                      J=8Hz)                                                      H    H            m.p., 92-94° C. (decomp.)                                              .sup.1 H-NMR (δ, d.sub.6 -DMSO):                                        3.2-4.0(br, 3H), 4.38(s,                                                      2H), 6.55(d, 1H, J=12Hz),                                                     6.77(d, 1H, J=8Hz),                                                           10-11(br, 1H)                                               H    C.sub.2 H.sub.5                                                                            m.p., 79-82° C. (decomp.)                            H    CH.sub.2 CHCH.sub.2                                                                        m.p., 69-71° C. (decomp.)                            CH.sub. 3                                                                          CH.sub.2 CCH m.p., 73-74° C. (decomp.)                            ______________________________________                                    

The aniline (X) can be produced by the method as disclosed in U.S. Pat.No. 4,640,707.

For the practical use of the tetrahydroindazolylbenzoxazine (I), it isusually formulated with conventional solid or liquid carriers ordiluents as well as surface active agents or auxiliary agents intoconventional preparation forms such as emulsifiable concentrates,wettable powders, suspensions and granules. The content of thetetrahydroindazolyl-benzoxazine (I) as the active ingredient in suchpreparation forms is normally within a range of about 0.005 to 80 % byweight, preferably of about 0.01 to 70 % by weight. Examples of thesolid carrier or diluent are fine powders or granules of kaolin clay,attapulgite clay, bentonite, terra alba, pyrophyllite, talc,diatomaceous earth, calcite, walnut powders, urea, ammonium sulfate andsynthetic hydrous silicate, etc. As the liquid carrier or diluent, theremay be exemplified aromatic hydrocarbons (e.g. xylene,methylnaphthalene), alcohols (e.g. isopropanol, ethylene glycol,cellosolve), ketones (e.g. acetone, cyclohexanone, isophorone), soybeanoil, cotton seed oil, dimethylsulfoxide, N,N-dimethylformamide,acetonitrile, water, etc.

The surface active agent used for emulsification, dispersion orspreading may be of any type, for instance, either anionic or non-ionic.Examples of the surface active agent include alkylsulfates,alkylarylsulfonates, dialkylsulfosuccinates, phosphates ofpolyoxyethylenealkylaryl ethers, polyoxyethylene alkyl ethers,polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene blockcopolymer, sorbitan fatty acid esters, polyoxyethylene sorbitan fattyacid esters, etc. Examples of the auxiliary agents includeligninsulfonates, sodium alginate, polyvinyl alcohol, gum arabic, CMC(carboxymethyl cellulose), PAP (isopropyl acid phosphate), etc.

Practical embodiments of the herbicidal composition according to thepresent invention ar illustratively shown in the following exampleswherein parts are by weight. The compound number of the activeingredient corresponds to the one in Table 1.

FORMULATION EXAMPLE 1

Fifty parts of Compound No. 1, 3 or 4, 3 parts of calciumligninsulfonate, 2 parts of sodium laurylsulfate and 45 parts ofsynthetic hydrous silicate are mixed well while being powdered to obtaina wettable powder.

FORMULATION EXAMPLE 2

Five parts of any one of Compound Nos. 1 to 14, 14 parts ofpolyoxyethylenestyrylphenyl ether, 6 parts of calciumdodecylbenzenesulfonate, 40 parts of xylene and 35 parts ofcyclohexanone are mixed well to obtain an emulsifiable concentrate.

FORMULATION EXAMPLE 3

Two parts of Compound No. 3 or 4, 1 part of synthetic hydrous silicate,2 parts of calcium ligninsulfonate, 30 parts of bentonite and 65 partsof kaolin clay are mixed well while being powdered. The mixture is thenkneaded with water, granulated and dried to obtain granules.

FORMULATION EXAMPLE 4

Twenty-five parts of Compound No. 4 or 5 are mixed with 3 parts ofpolyoxyethylene sorbitan monooleate, 3 parts of carboxymethyl celluloseand 69 parts of water and pulverized until the particle size of themixture becomes less than 5 microns to obtain a suspension.

FORMULATION EXAMPLE 5

0.03 Part of Compound No. 4, 1 part of synthetic hydrous silicate, 2parts of calcium ligninsulfonate, 30 parts of bentonite and 66.97 partsof kaolin clay are mixed well while being powdered. The mixture is thenkneaded with water, granulated and dried to obtain granules.

The tetrahydroindazolyl-benzoxazine (I) thus formulated in any suitablepreparation form is useful for pre-emergence or post-emergence controlof undesired weeds by soil or foliar treatment as well as floodfallowing treatment. These treatments include application to the soilsurface prior to or after transplanting, incorporation into the soil,etc. The foliar treatment may be effected by spraying the herbicidalcomposition containing the tetrahydroindazolyl-benzoxazine (I) over thetop of plants. It may also be applied directly to the weeds if care istaken to keep the chemical off the crop foliage.

The tetrahydroindazolyl-benzoxazine (I) may be used together with anyother herbicide to improve its activity as a herbicide, and in somecases, a synergistic effect can be expected. Further, it may be appliedin combination with an insecticide, an acaricide, a nematocide, afungicide, a plant growth regulator, a fertilizer, a soil improver, etc.Furthermore, it may be used as a herbicide applicable to agriculturalplowed fields as well as paddy fields. It is also useful as a herbicideto be employed for orchards, pasture lands, lawns, forests,non-agricultural fields, etc.

The dosage of the tetrahydroindazolyl-benzoxazine (I) may vary dependingon the prevailing weather conditions, the formulation used, theprevailing season, the mode of application, the soil involved, the cropand weed species, etc. Generally, however, the dosage is from about 0.01to 80 grams, preferably from about 0.02 to 40 grams, of the activeingredient per are. The herbicidal composition of the inventionformulated in the form of an emulsifiable concentrate, a wettable powderor a suspension may ordinarily be employed by diluting it with water ata volume of about 1 to 10 liters per are, if necessary, with addition ofan auxiliary agent such as a spreading agent. Examples of the spreadingagent include, in addition to the surface active agents as noted above,polyoxyethylene resin acid (ester), ligninsulfonate, abietylenic acidsalt, dinaphthylmethanedisulfonate, paraffin, etc. The compositionformulated in the form of granules may be normally applied as suchwithout dilution.

The biological data of the tetrahydroindazolylbenzoxazines (I) asherbicides will be illustratively shown in the following Exampleswherein the phytotoxicity to crop plants and the herbicidal activity onweeds were observed visually as to the degree of germination as well asthe growth inhibition and rated with an index 0, 1, 2, 3, 4 or 5, thenumeral "0" indicating no material difference as seen in comparison withthe untreated plants and the numeral "5" indicating the completeinhibition or death of the test plants.

The compounds as shown in Table 4 were used for comparison.

                                      TABLE 4                                     __________________________________________________________________________    Compound                                                                      No.   Structure           Remarks                                             __________________________________________________________________________           ##STR11##          Commercially available herbicide "chloronitrofen                              "                                                   B                                                                                    ##STR12##          U.S. Pat. No. 4,640,707                             C                                                                                    ##STR13##          U.S. Pat. No. 4,640,707                             D                                                                                    ##STR14##          U.S. Pat. No. 4,670,043                             __________________________________________________________________________

TEST EXAMPLE 1

Cylindrical plastic pots (diameter, 10 cm; height, 10 cm) were filledwith upland field soil, and the seeds of Japanese millet, oats, tallmorningglory and velvetleaf were sowed therein and covered with soil. Adesignated amount of the test compound formulated in an emulsifiableconcentrate as in Formulation Example 2 was diluted with water, and thedilution was sprayed onto the soil surface by means of a small handsprayer at a spray volume of 10 liters per are. The test plants weregrown in a greenhouse for 20 days, and the herbicidal activity wasexamined. The results are shown in Table 5.

                  TABLE 5                                                         ______________________________________                                                   Herbicidal activity                                                                                Tall                                          Compound                                                                              Dosage   Japanese       morning                                                                              Velvet-                                No.     (g/are)  millet   Oats  glory  leaf                                   ______________________________________                                        1       5        5        5     5      5                                      2       5        5        5     5      5                                      3       5        5        5     5      5                                      4       5        5        5     5      5                                      5       5        5        5     5      5                                      6       5        4        --    5      5                                      7       5        5        5     5      5                                      8       5        5        4     5      5                                      9       5        5        --    5      5                                      10      5        5        5     5      5                                      11      5        5        5     5      5                                      12      5        5        5     5      5                                      13      5        5        5     5      5                                      14      5        5        5     5      5                                      A       5        0        0     0      0                                      ______________________________________                                    

TEST EXAMPLE 2

Cylindrical plastic pots (diameter, 10 cm; height, 10 cm) were filledwith upland field soil, and the seeds of Japanese millet, tallmorningglory, radish and velvetleaf were sowed therein and cultivated ina greenhouse for 10 days. A designated amount of the test compoundformulated in an emulsifiable concentrate as in Formulation Example 2was diluted with water containing a spreading agent, and the dilutionwas sprayed over the foliage of the test plant by means of a small handsprayer at a spray volume of 10 liters per are. The test plants werefurther grown in the greenhouse for 20 days, and the herbicidal activitywas examined. The results are shown in Table 6.

                  TABLE 6                                                         ______________________________________                                                   Herbicidal activity                                                                          Tall                                                Compound                                                                              Dosage   Japanese morning-      Velvet-                               No.     (g/are)  millet   glory  Radish leaf                                  ______________________________________                                        1       5        5        5      5      5                                             1.25     5        5      5      5                                     2       5        5        5      5      5                                             1.25     5        5      5      5                                     3       5        5        5      5      5                                             1.25     5        5      5      5                                     4       5        5        5      5      5                                             1.25     5        5      5      5                                     5       5        5        5      5      5                                             1.25     5        5      5      5                                     6       5        5        5      5      5                                     7       5        5        5      5      5                                             1.25     5        5      5      5                                     8       5        5        5      5      5                                             1.25     5        5      5      5                                     9       5        5        5      5      5                                     10      5        5        5      5      5                                     11      5        5        5      5      5                                     12      5        5        5      5      5                                     13      5        5        5      5      5                                     14      5        5        5      5      5                                     A       5        2        2      0      3                                             1.25     0        0      0      0                                     ______________________________________                                    

TEST EXAMPLE 3

Cylindrical plastic pots (diameter, 8 cm,; height, 12 cm) were filledwith paddy field soil, and the seeds of barnyardgrass (Echinochloaoryzicola), broad-leaved weeds (i.e. common falsepimpernel, indiantoothcup, waterwort) were sowed in 1 to 2 cm depth. Water was pouredtherein to make a flooded condition, and rice seedlings of 3-leaf stagewere transplanted therein, and the test plants were grown in agreenhouse. Six days (at that time weeds began to germinate) thereafter,a designated amount of the test compound formulated in an emulsifiableconcentrate as in Formulation Example 2 and diluted with water (5 ml)was applied to the pots by perfusion. The test plants were grown for anadditional 20 days in the greenhouse, and the herbicidal activity wasexamined. The results are shown in Table 7.

                  TABLE 7                                                         ______________________________________                                                    Herbicidal activity                                               Compound Dosage   Rice    Barnyard-                                                                              Broad-leaved                               No.      (g/are)  plant   grass    weed                                       ______________________________________                                        1        0.08     --      5        5                                          2        0.08     1       5        5                                          3        0.08     1       5        5                                          4        0.08     0       5        5                                          5        0.08     0       5        5                                          7        0.08     1       5        5                                          8        0.08     1       5        5                                          9        0.08     0       5        5                                          A        0.08     0       0        0                                          B        0.08     0       1        2                                          ______________________________________                                    

TEST EXAMPLE 4

Vats (33 cm×23 cm×11 cm) were filled with upland field soil, and theseeds of soybean, corn, tall morningglory, velvetleaf, Slender amaranth,black nightshade and green foxtail were sowed therein in 1 to 2 cmdepth. A designated amount of the test compound formulated in anemulsifiable concentrate as in Formulation Example 2 was diluted withwater, and the dilution was sprayed onto the soil surface by means of asmall hand sprayer at a spray volume of 10 liters per are. The testplants were grown in a greenhouse for 20 days, and the herbicidalactivity was examined. The results are shown in Table 8.

                                      TABLE 8                                     __________________________________________________________________________              Phyto-                                                                              Herbicidal activity                                                     toxicity                                                                            Tall           Black                                          Compound                                                                            Dosage                                                                            Rice  morning-                                                                           Velvet-                                                                            Slender                                                                            night-                                                                            Green                                      No.   (g/are)                                                                           plant                                                                            Corn                                                                             glory                                                                              leaf amaranth                                                                           shade                                                                             foxtail                                    __________________________________________________________________________    1     5   1  1  5    5    5    5   5                                          2     5   0  1  5    5    5    5   4                                          3     5   0  0  5    5    5    5   5                                          4     2.5 1  1  5    5    5    5   5                                          5     5   0  1  5    5    5    5   5                                          A     5   0  0  0    1    1    1   0                                          D     2.5 1  5  5    5    5    5   5                                          __________________________________________________________________________

TEST EXAMPLE

Vats (33 cm×23 cm×11 cm) were filled with upland field soil, and theseeds of corn, common cocklebur, velvetleaf, tall morningglory and blacknightshade were sowed therein and cultivated for 18 days in agreenhouse. A designated amount of the test compound formulated in anemulsifiable concentrate as in Formulation Example 2 was diluted withwater containing a spreading agent, and the dilution was sprayed overthe foliage of the test plants by means of a small hand sprayer at aspray volume of 10 liters per are. The test plants were further grown inthe greenhouse for 20 days, and the herbicidal activity was examined. Atthe time of the application, the test plants were generally at the 1 to4 leaf stage and in 2 to 12 cm height, although the growing stage of thetest plants varied depending on their species. The results are shown inTable 9.

                                      TABLE 9                                     __________________________________________________________________________               Herbicidal activity                                                                           Tall Black                                         Compound                                                                            Dosage   Common                                                                              Velvet-                                                                             morning-                                                                           night-                                        No.   (g/are)                                                                            Corn                                                                              cocklebur                                                                           leaf  glory                                                                              shade                                         __________________________________________________________________________    3     0.32 1   4     5     5    5                                             4     0.32 1   5     5     5    5                                             A     0.32 0   0     0     0    0                                             D     0.32 3   5     5     5    5                                             __________________________________________________________________________

TEST EXAMPLE 6

Wagner's pots (1/5000 are) were filled with paddy field soil, and theseeds of barnyardgrass (Echinochloa oryzicola), broad-leaved weeds (i.e.common falsepimpernel, indian toothcup, waterwort) were sowed in 1 to 2cm depth. Water was poured therein to make a flooded condition, and riceseedlings of 3-leaf stage were transplanted therein, and the test plantswere grown in a greenhouse. Four days (at that time barnyardgrass beganto germinate) thereafter a designated amount of the test compoundformulated in an emulsifiable concentrate as in Formulation Example 2and diluted with water (10 ml) was applied to the pots by perfusion. Thetest plants were grown for an additional 20 days in the greenhouse, andthe herbicidal activity was examined. The results are shown in Table 10.At the time of the treatment, the depth of water in the pots was kept at4 cm and following two days, water was permitted to leak a volumecorresponding to a 3 cm depth per day.

                  TABLE 10                                                        ______________________________________                                                    Herbicidal activity                                               Compound Dosage   Rice    Barnyard-                                                                              Broad-leaved                               No.      (g/are)  plant   grass    weed                                       ______________________________________                                        1        0.04     1       5        5                                          2        0.04     1       5        5                                          3        0.04     1       5        5                                          4        0.04     1       5        5                                          A        0.04     0       0        0                                          B        0.04     0       0        1                                          ______________________________________                                    

TEST EXAMPLE 7

Wagner's pots (1/5000 are) were filled with paddy field soil, and theseeds of barnyardgrass (Echinochloa oryzicola), broad-leaved weeds (i.e.common falsepimpernel, indian toothcup, waterwort) were sowed in 1 to 2cm depth. Water was poured therein to make a flooded condition, and riceseedlings of 2-leaf stage were transplanted therein, and the test plantswere grown in a greenhouse. Five days (at that time weeds began togerminate) thereafter, a designated amount of the test compoundformulated in an emulsifiable concentrate as in Formulation Example 2and diluted with water (10 ml) was applied to the pots by perfusion. Thetest plants were grown for an additional 20 days in the greenhouse, andthe herbicidal activity was examined. The results are shown in Table 11.At the time of the treatment, the depth of water in the pots was kept at4 cm and following two days, water was permitted to leak a volumecorresponding to a 3 cm depth per day.

                  TABLE 11                                                        ______________________________________                                                    Herbicidal activity                                               Compound Dosage   Rice    Barnyard-                                                                              Broad-leaved                               No.      (g/are)  plant   grass    weed                                       ______________________________________                                        1        0.08     1       5        5                                                   0.02     0       5        5                                                   0.005    0       4        2                                          2        0.08     1       5        5                                                   0.02     0       5        5                                                   0.005    0       3        2                                          3        0.08     1       5        5                                                   0.02     0       5        5                                                   0.005    0       5        4                                          4        0.08     1       5        5                                                   0.02     0       5        5                                                   0.005    0       5        4                                                   0.0025   0       3        1                                          5        0.08     1       5        5                                                   0.02     0       5        4                                                   0.005    0       3        1                                          7        0.08     1       5        5                                                   0.02     0       5        4                                                   0.005    0       3        1                                          10       0.08     0       5        5                                                   0.02     0       5        5                                                   0.005    0       3        3                                          11       0.08     0       5        5                                                   0.02     0       5        5                                                   0.005    0       3        2                                          14       0.08     0       5        5                                                   0.02     0       5        5                                                   0.005    0       3        3                                          B        0.08     1       3        2                                                   0.02     0       0        0                                          C        0.08     1       5        4                                                   0.02     0       3        2                                                   0.005    0       0        0                                          D        0.08     2       5        5                                                   0.02     1       4        5                                                   0.005    0       3        3                                                   0.0025   0       0        0                                          ______________________________________                                    

What is claimed is:
 1. A compound of the formula: ##STR15## wherein R²is a hydrogen atom or a methyl group and R⁴ is a hydrogen atom, a C₁ -C₆alkyl group, a C₃ -C₇ alkenyl group, a C₃ -C₇ alkynyl group, a halo(C₁-C₅)alkyl group, a halo(C₃ -C₄)alkenyl group, a halo (C₃ -C₄)alkynylgroup, a C₁ -C₄ alkoxy(C₁ -C₂)alkyl group or a C₁ -C₂ alkylthio(C₁-C₂)alkyl group.
 2. The compound according to claim 1, wherein R² is ahydrogen atom.
 3. The compound according to claim 1, wherein R⁴ is ahydrogen atom, a C₃ -C₄ alkenyl group, a C₃ -C₄ alkynyl group, a halo(C₁-C₅)alkyl group or a halo(C₃ -C₄)alkenyl group.
 4. The compoundaccording to claim 1, wherein R⁴ is a hydrogen atom, a C₃ -C₄ alkynylgroup or a halo(C₃ -C₄)alkenyl group.
 5. The compound according to claim1, wherein R⁴ is a C₃ -C₄ alkynyl group or a halo(C₃ -C₄)alkenyl group.6. The compound according to claim 1, wherein R² is a hydrogen atom andR⁴ is a C₃ -C₇ alkynyl group.
 7. The compound according to claim 1,wherein R² is a hydrogen atom and R⁴ is a propargyl group.
 8. Thecompound according to claim 1, wherein R² and R⁴ are both hydrogenatoms.
 9. The compound according to claim 1, wherein R² is a hydrogenatom and R⁴ is an ethyl group.
 10. The compound according to claim 1,wherein R² is a hydrogen atom and R⁴ is a propenyl group.
 11. Thecompound according to claim 1, wherein R² is a methyl group and R⁴ is apropargyl group.